Dye mixtures, 1:2 cobalt complex formazan dyes and their use

ABSTRACT

Dye mixtures which comprise at least one 1:2 cobalt complex dye of the formazan compound of the formula  
                 
 
     in which X is substituted or unsubstituted C 1 -C 8 alkyl, phenyl, naphthyl, furyl or thienyl,  
     R 1  and R 2  independently of one another are hydrogen or substituted or unsubstituted C 1 -C 8 alkyl, phenyl or naphthyl,  
     m is a number from 1 to 4 and  
     the rings I, II, III and IV may be further substituted,  
     together with at least one anthraquinone dye of the formula (2) as defined in claim  1,  or together with at least one 1:2 chromium or 1:2 cobalt complex dye of two identical or different azo compounds from the group comprising the compounds of the formulae (3), (4), (5) and (6) as defined in claim  1;    
     and novel 1:2 cobalt complex formazan dyes.  
     The dye mixtures are particularly suitable for dyeing or printing natural and synthetic polyamide fiber materials, dyeings or prints having good fastnesses being obtained.

[0001] The present invention relates to mixtures of 1:2 cobalt complexformazan dyes with anthraquinone dyes or 1:2 chromium or 1:2 cobaltcomplex azo dyes, which are particularly suitable for dyeing or printingnatural or synthetic textile polyamide fibre materials and in particularhave very good fastness properties. The present invention furthermorerelates to the novel 1:2 cobalt complex formazan dyes.

[0002] The present invention relates to dye mixtures which comprise atleast one 1:2 cobalt complex dye of the formazan compound of the formula

[0003] in which X is substituted or unsubstituted C₁-C₈alkyl, phenyl,naphthyl, furyl or thienyl,

[0004] R₁ and R₂ independently of one another are hydrogen orsubstituted or unsubstituted C₁-C₈alkyl, phenyl or naphthyl,

[0005] m is a number from 1 to 4 and

[0006] the rings I, II, III and IV may be further substituted,

[0007] together with at least one anthraquinone dye of the formula (2)

[0008] in which Y is hydrogen or substituted or unsubstitutedC₁-C₈alkyl, cyclohexyl, phenyl or 1,2,3,4-tetrahydronaphthyl and

[0009] Z is substituted or unsubstituted C₁-C₈alkyl, cyclohexyl, phenylor 1,2,3,4-tetrahydronaphthyl,

[0010] and in which the ring V of the anthraquinone dye of the formula(2) may be further substituted by one or two hydroxyl groups,

[0011] or together with at least one 1:2 chromium or 1:2 cobalt complexdye of two identical or different azo compounds from the groupcomprising compounds of the formulae (3), (4), (5) and (6)

[0012] in which R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅and R₁₆ independently of one another are hydrogen, C₁-C₄alkyl,C₁-C₄alkoxy, C₂-C₄alkanoylamino, halogen, sulfo, hydroxyl, nitro,sulfamoyl or N—C₁-C₄alkylsulfamoyl, which is unsubstituted or furthersubstituted in the alkyl moiety part by hydroxyl or C₁-C₄alkoxy.

[0013] The 1:2 cobalt complex formazan dyes of the formula (1) arepreferably symmetric cobalt complex dyes.

[0014] Substituents of a phenyl, naphthyl, furyl or thienyl radical Xand of rings I, II, III and IV of the formazan compound of the formula(1) are, in addition to the radical of the formula —SO₂N(R₁)R₂,independently of one another, for example, C₁-C₄alkyl, for examplemethyl or ethyl; C₁-C₄alkoxy, for example methoxy or ethoxy;unsubstituted or halogen-substituted C₂-C₄alkanoylamino, for exampleacetylamino, propionylamino or α,β-dibromopropionylamino; hydroxyl;sulfo; nitro; carboxyl; cyano; amino; halogen, for example fluorine,chlorine or bromine; C₁-C₄alkylsulfonyl which is unsubstituted orsubstituted in the alkyl moiety by hydroxyl or C₁-C₄alkoxy;vinylsulfonyl; α-halogenoacryloylamino; radicals of the formulae —OR,—NHCOR′, —COOR″, CONHR′″ and SO₂R″″, in which R, R′, R″, R′″ and R″″independently of one another are phenyl or naphthyl and R′ canadditionally be C₁-C₄alkyl; or triazinylamino, which can be furthersubstituted by halogen, C₁-C₄alkylamino, phenylamino orN-C₁-C₄alkyl-N-phenylamino. The phenyl or naphthyl radicals mentionedcan be substituted as defined above for X and the rings I, II, III andIV, in particular by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino,hydroxyl, sulfo, nitro, carboxyl, cyano, halogen or C₁-C₄alkylsulfonylwhich is unsubstituted or further substituted in the alkyl moiety byhydroxyl or C₁-C₄alkoxy.

[0015] In addition to the radical of the formula —SO₂N(R₁)R₂, preferredsubstituents for X and the rings I, II, III and IV of the formazancompound of the formula (1) are C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl, C₁-C₄hydroxyalkylsulfonyl,halogen, sulfo, hydroxyl, carboxyl and nitro.

[0016] X is preferably phenyl, which can be substituted, for example, asdefined above.

[0017] Phenyl or naphthyl radicals R₁ and R₂ can be unsubstituted orsubstituted. Examples of such substituents are C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl, halogen, sulfo, hydroxyl,carboxyl, nitro, sulfamoyl and N—C₁-C₄alkylsulfamoyl which isunsubstituted or further substituted in the alkyl moiety by hydroxyl orC₁-C₄alkoxy.

[0018] C₁-C₈alkyl radicals X, R₁ and R₂ independently of one anotherare, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl, and thecorresponding radicals which are substituted, for example, by hydroxyl,C₁-C₄alkoxy or halogen. C₁-C₄alkyl, which can be substituted as defined,is preferred here.

[0019] R₁ and R₂ are preferably independently of one another hydrogen,C₁-C₈alkyl or phenyl, where the alkyl and phenyl radicals can besubstituted as defined above.

[0020] R₁ and R₂ are preferably independently of one another hydrogen,C₁-C₄alkyl which is unsubstituted or substituted by hydroxyl orC₁-C₄alkoxy, or phenyl which is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl,C₁-C₄hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl, nitro,sulfamoyl or N—C₁-C₄alkylsulfamoyl which is unsubstituted or furthersubstituted in the alkyl moiety by hydroxyl or C₁-C₄alkoxy. Inparticular, one of the radicals R₁ and R₂ is hydrogen here.

[0021] R₁ and R₂ are particularly preferably hydrogen, C₁-C₄alkyl whichis unsubstituted or substituted by hydroxyl, or phenyl which isunsubstituted or substituted by sulfo, carboxyl or sulfamoyl. Inparticular, one of the radicals R₁ and R₂ is hydrogen here. R₁ and R₂are especially preferably independently of one another hydrogen orC₁-C₄alkyl, in particular hydrogen or methyl.

[0022] m is preferably the number 1 or 2, in particular the number 2.

[0023] Substituents of phenyl radicals Y and Z are, for example:C₁-C₁₂alkyl; C₁-C₄alkoxy; C₂-C₄alkanoylamino; hydroxyl; sulfo; nitro;carboxyl; cyano; amino; halogen; benzoylaminomethyl; chloroacetylamino;chloroacetylaminomethyl; α-chloroacryloylaminomethyl;acryloylaminomethyl; or phenoxy, phenylcarbonylamino, phenylsulfonyloxy,phenylsulfonylamino, phenylsulfonylaminomethyl orN-methyl-phenylsulfonylaminomethyl, where the phenyl radicals can befurther substituted as defined above for Y and Z. The radical Zfurthermore can be an anthraquinone dye radical bonded via a bridgemember, examples of these are the anthraquinone dyes of the followingformula (11).

[0024] C₁-C₈alkyl radicals Y and Z independently of one another are, forexample, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, pentyl, hexyl, heptyl or octyl, where the alkyl radicals canbe substituted by phenyl and the phenyl radical can be furthersubstituted as defined above for phenyl radicals Y and Z. Preferredsubstituents of the phenyl radical here are C₁-C₁₂alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, hydroxyl, sulfo, nitro, carboxyl, cyano, amino,halogen, benzoylaminomethyl, chloroacetylamino, chloroacetylaminomethyl,a-chloroacryloylaminomethyl or acryloylaminomethyl.

[0025] Cyclohexyl radicals Y and Z independently of one another are, inaddition to unsubstituted cyclohexyl, cyclohexyl substituted, forexample, by C₁-C₄alkyl, phenylsulfonylamino or benzyl, where the phenylradicals can be further substituted, for example, by C₁-C₄alkyl,C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo or halogen.

[0026] 1,2,3,4-Tetrahydronaphthyl radicals Y and Z independently of oneanother are, in addition to unsubstituted 1,2,3,4-tetrahydronaphthyl,the radical substituted, for example, by sulfo.

[0027] If the anthraquinone dye of the formula (2) contains one or twohydroxyl groups in ring V, these are as a rule bonded in the 1- and/or2-position.

[0028] The total number of sulfo groups in the anthraquinone dye of theformula (2) is one or two.

[0029] C₁-C₄alkyl radicals R₃ to R₁₆ independently of one another aremethyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl ortert-butyl, in particular methyl.

[0030] C₁-C₄alkoxy radicals R₃ to R₁₆ independently of one another aremethoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy ortert-butoxy, in particular methoxy.

[0031] C₂-C₄Alkanoylamino radicals R₃ to R₁₆ independently of oneanother are, for example, acetylamino or propionylamino, in particularacetylamino.

[0032] Halogen atoms R₃ to R₁₆ independently of one another are, forexample, fluorine, chlorine or bromine, in particular chlorine.

[0033] The formazan compounds of the formula (1) are preferablycompounds of the formula

[0034] in which R₁, R₂ and m are as defined and preferred above; and

[0035] the phenyl radicals can contain no further substituents or arefurther substituted as defined above for rings I, II, III and IV.Preferably, the phenyl radicals of the compound of the formula (7) maybe further substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino,C₁-C₄alkylsulfonyl, C₁-C₄hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl,carboxyl or nitro.

[0036] The formazan compounds of the formula (1) are particularlypreferably compounds of the formula

[0037] in which R₁ and R₁′ independently of one another are hydrogen orC₁-C₄alkyl and the phenyl radicals contain no further substituents orcan be further substituted as defined above for rings I, II, III and IV.Preferably, the phenyl radicals of the compound of the formula (8) maybe further substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino,C₁-C₄alkylsulfonyl, C₁-C₄hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl,carboxyl or nitro. The phenyl radicals of the compound of the formula(8) preferably contain no further substituents.

[0038] The formazan compounds of the formula (1) are especiallypreferably compounds of the formula

[0039] in which the phenyl radicals contain no further substituents orcan be further substituted as defined above for the compound of theformula (8). Preferably, the phenyl radicals of the compound of theformula (8a) contain no further substituents.

[0040] Preferred anthraquinone dyes of the formula (2) are anthraquinonedyes of the formula

[0041] in which Z₁ is phenyl which is unsubstituted or substituted byC₁-C₁₂alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, halogen,benzoylaminomethyl, chloroacetylamino, chloroacetylaminomethyl orα-chloroacryloylaminomethyl; phenyl-C₁-C₈alkyl, where the phenyl radicalcontains no further substituents or is substituted as defined for aphenyl radical Z, under formula (9); cyclohexyl which is unsubstitutedor substituted by C₁-C₄alkyl, phenylsulfonylamino orC₁-C₄alkylphenylsulfonylamino; 1,2,3,4-tetrahydronaphthyl; or a radicalof the formula

[0042] in which W is a bridge member of the formula —O—, —NH—CO—,—OSO₂—, —NH—SO₂—, —CH₂—NH—SO₂— or —CH₂—N(CH₃)—SO₂—,

[0043] R₁₇ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or halogen and

[0044] R₁₈ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, halogen oracryloylaminomethyl,

[0045] Y₁ is hydrogen; C₁-C₄alkyl; phenyl which is unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen; phenyl-C₁-C₈alkylwhich is unsubstituted or substituted in the phenyl ring by C₁-C₄alkyl,C₁-C₄alkoxy, halogen or benzoylaminomethyl; cyclohexyl which isunsubstituted or substituted by C₁-C₄alkyl; or1,2,3,4-tetrahydronaphthyl, or anthraquinone dyes of the formula

[0046] in which Z₂ is phenyl which is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy or halogen or cyclohexyl which is unsubstitutedor substituted by C₁-C₄alkyl or benzyl and

[0047] Y₂ is C₁-C₄alkyl or is as defined above for Z₂,

[0048] or anthraquinone dyes of the formula

[0049] in which R₁₉ and R₂₀ are hydrogen or methyl.

[0050] Particularly preferred anthraquinone dyes of the formula (2) areanthraquinone dyes of the formula

[0051] 1:2 or 1:2 cobalt complex azo dyes are, in particular, 1:2 cobaltcomplex dyes of two identical or different azo compounds from the groupcomprising compounds of the formulae (3), (4) and (5), and 1:2 chromiumcomplex dyes of two identical or different azo compounds from the groupcomprising compounds of the formulae (5) and (6).

[0052] Particularly preferred 1:2 chromium or 1:2 cobalt complex azodyes are dyes of the formula

[0053] Especially preferred dye mixtures are those which comprise, inaddition to the 1:2 cobalt complex formazan dye, at least one dye of theformulae (9), (10), (11) and (43) to (50), in particular at least onedye of the formulae (12) to (50). The dye of the formula (50) isespecially preferred here. The 1:2 cobalt complex formazan dye here isas defined and preferred above.

[0054] The anthraquinone dyes of the formula (2) and the 1:2 chromiumand 1:2 cobalt complex azo dyes are known or can be obtained analogouslyto known compounds. Thus, anthraquinone dyes of the formula (2) can beobtained, for example, analogously to processes defined in GB-A-903 590,GB-A-945 806, GB-A-2 009 214 and U.S. Pat. No. 3,491,125. The 1:2chromium and 1:2 cobalt complex azo dyes can be obtained, for example,analogously to processes defined in GB-A-716 753, GB-A-719 274, GB-A-745641 and GB-A-851 861.

[0055] Some of the 1:2 cobalt complex formazan dyes of the formula (1)are novel. The 1:2 cobalt complex formazan dyes of the formula (1) canbe obtained analogously to the process defined for the preparation ofthe novel 1:2 cobalt complex formazan dyes.

[0056] The dye mixture according to the invention can be prepared, forexample, by mixing the individual dyes. This mixing process is carriedout, for example, in suitable mills, for example bead and pinned discmills, and in kneaders or mixers.

[0057] The dye mixtures furthermore can be prepared, for example, byspray drying the aqueous dye mixtures.

[0058] The dye mixtures preferably comprise 5 to 95% by weight, inparticular 10 to 90% by weight and preferably 20 to 80% by weight, ofthe 1:2 cobalt complex formnazan dye, based on the total amount of thedyes of the mixtures.

[0059] If they contain sulfo groups, the individual dyes are present inthe dye mixtures according to the invention either in the form of theirfree sulfonic acid or, preferably, as salts thereof, for example alkalimetal, alkaline earth metal or ammonium salts or as salts of an organicamine. Examples are the sodium, lithium or ammonium salts or the salt oftriethanolamine. Counter-ions of metal complex dyes having a negativecharge are, for example, the cations of the abovementioned salts.

[0060] The dye mixtures as a rule contain further additives, for examplesodium chloride or dextrin.

[0061] The invention furthermore relates to a process for dyeing orprinting fibre materials containing hydroxyl groups or containingnitrogen using the dye mixtures according to the invention.

[0062] Fibre materials are preferably both natural polyamide fibrematerials, for example silk or, in particular, wool, and syntheticpolyamide fibre materials, for example polyamide 6 or polyamide 6.6, orwool- or polyamide-containing blend fabrics. Synthetic polyamide fibrematerials are of particular interest here.

[0063] The fibre material mentioned can be in widely varying processingforms, for example as fibres, yarn, woven fabric or knitted fabric, andin particular in the form of carpets.

[0064] The dyeing or printing can be carried out in customary dyeing orprinting apparatuses. The dye liquors or printing pastes can comprisefurther additives, for example wetting agents, antifoams, levellingagents or agents which influence the property of the textile material,for example softening agents, additives for flameproofing or soil-,water- and oil-repellent agents, as well as water-softening agents andnatural or synthetic thickeners, for example alginates and celluloseethers.

[0065] The dye mixtures according to the invention give level dyeingshaving good all-round properties, in particular good fastness torubbing, wet processing, wet rubbing, light and hot light. The dyemixtures according to the invention furthermore have a goodwater-solubility and resistance to hard water and are distinguished bygood affinity properties and good combinability with other dyes.

[0066] The invention furthermore relates to symmetric 1:2 cobalt complexformazan dyes of compounds of the formula

[0067] in which R₂₁ is hydrogen, halogen or C₁-C₄alkylsulfonyl which isunsubstituted or hydroxyl-substituted and

[0068] a) A₁ is a radical of the formula

[0069] B₁ is a radical of the formula

[0070] in which R₂₂ is hydrogen or unsubstituted or hydroxyl-substitutedC₁-C₄alkyl,

[0071] R₂₂′ is hydrogen or C₁-C₄alkyl,

[0072] R₂₃ and R₂₃′ independently of one another are each hydrogen,C₁-C₄alkyl or halogen,

[0073] R₂₄ is C₁-C₄alkanoylamino or N—C₁-C₄alkylsulfamoyl which isunsubstituted or substituted in the alkyl moiety by hydroxyl,

[0074] R₂₅ is hydrogen or halogen and

[0075] R₂₆ is hydrogen, unsubstituted or hydroxyl-substituted C₁-C₄alkylor phenyl which is unsubstituted or substituted by sulfo, carboxyl orsulfamoyl, or

[0076] b) A₁ is a radical of the formula

[0077] B₁ is a radical of the formula

[0078] in which R₂₇ is hydrogen or halogen,

[0079] R₂₈ is hydrogen or sulfamoyl and

[0080] R₂₅ and R₂₆ independently are as defined above.

[0081] C₁-C₄alkyl here is generally methyl, ethyl, n- or iso-propyl orn, iso-, sec- or tert-butyl, and preferably methyl or ethyl. Examples ofunsubstituted or hydroxyl-substituted C₁-C₄alkyl are, in particular,methyl, ethyl or 2-hydroxyethyl. Halogen is generally, for example,fluorine, bromine or, in particular, chlorine. Examples of unsubstitutedor hydroxyl-substituted C₁-C₄alkylsulfonyl are methylsulfonyl,ethylsulfonyl or 2-hydroxyethylsulfonyl. Examples of C₁-C₄alkanoylaminoare acetylamino or propionylamino.

[0082] Preferred embodiments of the present invention relate to:

[0083] a) symmetric 1:2 cobalt complex formazan dyes of compounds of theformula

[0084] in which R₂₁ is hydrogen, chlorine or fluorine, R₂₂ is hydrogen,methyl, ethyl or 2-hydroxyethyl, R₂₅ is hydrogen or chlorine and R₂₆ ishydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl, 2- or 3-carboxyphenyl,2- or 3-sulfamoylphenyl or 2- or 3-sulfophenyl.

[0085] b) symmetric 1:2 cobalt complex formazan dyes of compounds of theformula (51a) defined above, in which R₂₁ is hydrogen, chlorine orfluorine, R₂₂ is hydrogen, methyl or ethyl, R₂₅ is chlorine and R₂₆ ishydrogen, methyl, ethyl, 2-carboxyphenyl, 2-sulfamoylphenyl or2-sulfophenyl.

[0086] c) symmetric 1:2 cobalt complex formazan dyes of compounds of theformula

[0087] in which R₂₁ is hydrogen or chlorine, R₂₂′ is hydrogen, methyl orethyl, R₂₄′ is N-methylsulfamoyl, N-ethylsulfamoyl orN-2-hydroxyethylsulfamoyl, R₂₅ is hydrogen or chlorine and R₂₆ ishydrogen, methyl or ethyl.

[0088] d) symmetric 1:2 cobalt complex formnazan dyes of compounds ofthe formula (51b) defined above, in which R₂₁ is hydrogen, R₂₂′ ishydrogen, R₂₄ is acetylamino or, in particular, propionylamino, R₂₅ ishydrogen or chlorine and R₂₆ is hydrogen, methyl or ethyl.

[0089] e) symmetric 1:2 cobalt complex formazan dyes of compounds of theformula

[0090] in which R₂₁ is hydrogen, methylsulfonyl, ethylsulfonyl or2-hydroxyethylsulfonyl, R₂₅ is hydrogen or chlorine, R₂₆ is hydrogen,methyl, ethyl, 2-sulfophenyl, 2-carboxyphenyl or 2-sulfamoylphenyl, R₂₇is hydrogen or chlorine and R₂₈ is hydrogen or sulfamoyl.

[0091] f) Symmetric 1:2 cobalt complex formazan dyes of the formula

[0092] in which M^(⊕) is a cation.

[0093] A cation M^(⊕) is, for example, a proton or, preferably, a metalcation, for example an alkali metal cation, such as Na^(⊕), K^(⊕) orLi^(⊕); M^(⊕) furthermore can be an ammonium cation or the ammonium saltof an organic amine, for example the salt of mono-, di- ortriethanolamine.

[0094] The compounds of the formula (51) can be prepared in a mannerwhich is known per se, for example by diazotizing a compound of theformula

B₁—NH₂   (57),

[0095] coupling the product to the hydrazone of the formula

[0096] and metallizing the resulting metal-free compound with a cobaltsalt, in which the variables R₂₁, A₁ and B₁ are as defined under formula(51).

[0097] The diazotization of the amine of the formula (57) is as a rulecarried out by the action of nitrous acid in aqueous-mineral acidsolution at a low temperature, and the coupling to the couplingcomponent of the formula (58) is advantageously carried out at alkalinepH values, for example at pH≧9 and in particular at a pH of 10 to 12.

[0098] The metallization takes place, for example, in an aqueous mediumwhich has an alkaline pH, for example a value of 7.5 to 12, andpreferably 8 to 12, at a temperature of 40 to 100° C., and in particularat 40 to 60° C. Suitable cobalt salts are, for example, the acetate,nitrate, chloride or, in particular, the sulfate.

[0099] The coupling of the diazotized compound of the formula (57) tothe compound of the formula (58) and the metallization can be carriedout in succession or also simultaneously, for example by adding thediazo suspension together with the cobalt salt to the solution of thehydrazone.

[0100] The compounds of the formulae (57) and (58) are known per se orcan be prepared analogously to known compounds.

[0101] The dyes according to the invention as a rule contain furtheradditives, for example sodium chloride or dextrin.

[0102] The invention furthermore relates to a process for dyeing orprinting fibre materials containing hydroxyl groups or containingnitrogen with the dyes according to the invention.

[0103] Preferred fibre materials are both natural polyamide fibrematerials, for example silk or, in particular, wool, and syntheticpolyamide fibre materials, for example polyamide 6 or polyamide 6.6, orwool- or polyamide-containing blend fabrics. Synthetic polyamide fibrematerials are of particular interest here.

[0104] The fibre material mentioned can be in widely varying processingforms, for example as fibres, yarn, woven fabric or knitted fabric, andin particular in the form of carpets.

[0105] The dyeing or printing can be carried out in customary dyeing orprinting apparatuses. The dye liquors or printing pastes can comprisefurther additives, for example wetting agents, antifoams, levellingagents or agents which influence the property of the textile material,for example softening agents, additives for flameproofing or soil-,water- and oil-repellent agents, as well as water-softening agents andnatural or synthetic thickeners, for example alginates and celluloseethers.

[0106] The dyes according to the invention give level dyeings havinggood all-round properties, in particular good fastness to rubbing, wetprocessing, wet rubbing, light and hot light. The dyes according to theinvention furthermore have a good water-solubility and resistance tohard water and are distinguished by good affinity properties and by goodcombinability with other dyes.

[0107] In the following examples, parts are by weight. The temperaturesare degrees Celsius. Parts by weight bear the same relation to parts byvolume as the gram to the cubic centimetre.

EXAMPLE 1A

[0108] For preparation of a dye mixture which comprises the dyes of theformulae

[0109] 55 parts of the dye of the formula (101), 13 parts of the dye ofthe formula (102), 14 parts of the dye of the formula (103) and 18 partsof the dye of the formula (104) are homogeneously mixed in a mixer togive 100 parts of the mixture called dye mixture A below.

EXAMPLE 1B

[0110] To prepare a dye mixture comprising the dyes of the formulae(101) and (103) and the dye of the formula

[0111] 22 parts of the dye of the formula (101), 47 parts of the dye ofthe formula (103) and 31 parts of the dye of the formula (105) arehomogeneously mixed in a mixer to give 100 parts of the mixture calleddye mixture B below.

EXAMPLE 1C

[0112] To prepare a dye mixture which comprises the dyes of the formulae(101), (102) and (103), 20 parts of the dye of the formula (101), 35parts of the dye of the formula (102) and 45 parts of the dye of theformula (103) are homogeneously mixed in a mixer to give 100 parts ofthe mixture called dye mixture C below.

EXAMPLE 1D

[0113] To prepare a dye mixture which comprises the dyes of the formulae(101) and (105) and the dye of the formula

[0114] 22 parts of the dye of the formula (101), 32 parts of the dye ofthe formula (105) and 46 parts of the dye of the formula (106) arehomogeneously mixed in a mixer to give 100 parts of the mixture calleddye mixture D below.

EXAMPLE 1E

[0115] To prepare a dye mixture which comprises the dyes of the formulae(101), (102) and (106), 21 parts of the dye of the formula (101), 36parts of the dye of the formula (102) and 43 parts of the dye of theformula (106) are homogeneously mixed in a mixer to give 100 parts ofthe mixture called dye mixture E below.

EXAMPLE 1F

[0116] To prepare a dye mixture which comprises the dyes of the formulae(101) and (106) and the dyes of the formulae

[0117] 40 parts of the dye of the formula (101), 7 parts of the dye ofthe formula (106), 40 parts of the dye of the formula (107) and 13 partsof the dye of the formula (108) are homogeneously mixed in a mixer togive 100 parts of the mixture called dye mixture F below.

EXAMPLE 1G

[0118] To prepare a dye mixture which comprises the dyes of the formulae(101), (106) and (107), 41 parts of the dye of the formula (101), 4parts of the dye of the formula (106) and 55 parts of the dye of theformula (107) are homogeneously mixed in a mixer to give 100 parts ofthe mixture called dye mixture G below.

EXAMPLE 1H

[0119] To prepare a dye mixture which comprises the dye of the formula(101) and the dye of the formula

[0120] 45 parts of the dye of the formula (101) and 55 parts of the dyeof the formula (109) are homogeneously mixed in a mixer to give 100parts of the mixture called dye mixture H below.

EXAMPLE 1I

[0121] To prepare a dye mixture which comprises the dye of the formula(101) and the dye of the formula

[0122] 45 parts of the dye of the formula (101) and 55 parts of the dyeof the formula (110) are homogeneously mixed in a mixer to give 100parts of the mixture called dye mixture I below.

EXAMPLE 1J

[0123] To prepare a dye mixture which comprises the dye of the formula(101), the dye of the formula

[0124] and the dye of the formula

[0125] 22 parts of the dye of the formula (101), 31 parts of the dye ofthe formula (111) and 47 parts of the dye of the formula (112) arehomogeneously mixed in a mixer to give 100 parts of the mixture calleddye mixture J below.

EXAMPLE 1K

[0126] To prepare a dye mixture which comprises the dye of the formula

[0127] and the dye of the formula

[0128] 30 parts of the dye of the formula (113) and 70 parts of the dyeof the formula (114) are homogeneously mixed in a mixer to give 100parts of the mixture called dye mixture K below.

EXAMPLE 1L

[0129] To prepare a dye mixture which comprises the dye of the formula(101) and the dye of the formula

[0130] 50 parts of the dye of the formula (101) and 50 parts of the dyeof the formula (115) are homogeneously mixed in a mixer to give 100parts of the mixture called dye mixture L below.

EXAMPLE 2

[0131] 86.1 g of 4-sulfamoylaniline are introduced into 200 ml of water,the pH is brought to about 11.5 with sodium hydroxide solution and themixture is heated at about 50° C. until a solution has formed. 125 ml of4N sodium nitrite solution are allowed to run rapidly into thissolution. After the temperature has dropped to about 35 to 40° C., theresulting solution is allowed to run into a cold mixture, at −5 to 0°C., of 100 g of ice and 400 ml of 31% naphthalene-1-sulfonic acidsolution. The mixture is kept at 0 to 2° C. for about 1 hour, a littlemore nitrite solution is added if appropriate, and at the end the excessnitrite is destroyed with sulfamic acid.

[0132] The pH of the solution obtained above is brought to 4.5 to 5 withsodium hydroxide solution, and a suspension of 104.6 g of sodiumpyrosulfite in 100 ml of water is then added dropwise at 0 to 5° C. inthe course of about 30 to 45 minutes; during this addition, the pH iskept at 6 to 6.5 by addition of sodium hydroxide solution. The mixtureis subsequently stirred at about 5° C. for 1 hour, at 40 to 50° C. for afurther 2 hours and finally at room temperature overnight. Afteraddition of HCl (pH≦1), the SO₂ formed is driven off with compressedair. The hydrazine-containing mixture is heated to 60 to 70° C. and 50ml of benzaldehyde are added dropwise in the course of about 15 minutes.The mixture is subsequently stirred at 65 to 70° C. for about 2 to 2.5hours and cooled to room temperature, and the compound which hascrystallized out, of the formula

[0133] is filtered off. After washing with water and hydrochloric acid,the product is dried in vacuo.

EXAMPLE 3

[0134] 30.3 g of 2-amino-4-N-methylsulfamoylphenol are dissolved in 180ml of water, the pH is rendered acid with HCl and the temperature iscooled to 0 to 5° C. 37.5 ml of 4N sodium nitrite solution are added atthis temperature and the amino compound is diazotized.

[0135] After the excess nitrite has been destroyed with sulfamic acidand the pH has been increased to 3 with sodium hydroxide solution, thediazo suspension is added in small portions, in the course of about 1.5hours, to a solution, which has been brought to pH 12.3 to 12.5 withsodium hydroxide solution, of 41.3 g of the hydrazone obtained accordingto Example 2 in about 350 ml of water at 40 to 45° C. and the pH is keptat 12.3 to 12.5 by addition of sodium hydroxide solution. The mixture issubsequently stirred at 40 to 45° C. for about 30 minutes, the pH islowered to about 9.5 with hydrochloric acid and the metal-free dye ofthe formula

[0136] is filtered off, after cooling, and washed with sodium chloridesolution.

EXAMPLE 4

[0137] The crude dye obtained according to Example 3 is homogeneouslysuspended in 600 ml of water and the suspension is heated to about 60 to70° C. The pH is brought to about 8.5 to 9.5 with sodium carbonatesolution, and 70 ml of 1 molar CoSO₄/tartaric acid solution are addeddropwise at 60 to 65° C. in the course of about 30 minutes, whilestirring, the pH being kept between 8.5 and 9 by addition of furthersodium carbonate solution. The colour shade changes from red to blue andthe 1:2 Co complex crystallizes out. The pH is brought to 11 to 11.5with sodium hydroxide solution, stirring is continued for about 30minutes, the pH is lowered to about 9.5 with hydrochloric acid, thecompound of the formula

[0138] is filtered off and the precipitate is washed with sodiumchloride solution.

EXAMPLE 5 to 34

[0139] The symmetric 1:2 cobalt complexes of compounds of the generalformula

[0140] in which the variables are as defined in the table, can beprepared analogously to those in Examples 2 to 4: Example No. A B C D E5 SO₂NH₂ H H SO₂NHCH₃ H 6 SO₂NH₂ H H H SO₂NH₂ 7 SO₂NH₂ H H SO₂NH₂ H 8SO₂NH₂ H H SO₂NHCH₃ Cl 9 SO₂NH₂ H H SO₂NH₂ Cl 10 SO₂NH₂ H H

H 11 SO₂NH₂ H Cl H

12 SO₂NHCH₃ H H H SO₂NH₂ 13 SO₂NH₂ H Cl SO₂NH₂ Cl 14 SO₂NH₂ H ClSO₂NHCH₃ Cl 15 SO₂NH₂ H F SO₂NH₂ Cl 16 SO₂NH₂ H F SO₂NHCH₃ Cl 17 HSO₂NH₂ H SO₂NH₂ Cl 18 H SO₂NH₂ H SO₂NHCH₃ Cl 19 H SO₂NH₂ H H

20 CH₃ SO₂NHC₂H₅OH H SO₂NH₂ Cl 21 CH₃ SO₂NHC₂H₅OH H SO₂NHCH₃ Cl 22 CH₃SO₂NHC₂H₅OH Cl SO₂NHCH₃ Cl 23 CH₃ SO₂NHC₂H₅OH Cl SO₂NH₂ Cl 24 H NHCOC₂H₅H H SO₂NH₂ 25 H NHCOC₂H₅ H H SO₂NHCH₃ 26 H NHCOC₂H₅ H SO₂NH₂ Cl 27 HNHCOC₂H₅ H SO₂NHCH₃ Cl 28 Cl H H SO₂NH₂ H 29 Cl H H SO₂NH₂ Cl 30 Cl H HSO₂NHCH₃ Cl 31 Cl H H

H 32 SO₂NH₂ H H H

33 H H SO₂C₂H₅OH SO₂NHCH₃ Cl 34 H SO₂NH₂ H

H

EXAMPLES 35 to 38

[0141] The symmetric 1:2 cobalt complexes of the compounds of thegeneral formula

[0142] in which the variables C and D are as defined in the table, canbe prepared analogously to those in Examples 2 to 4: Example No. C D 35H SO₂NH₂ 36 H SO₂NHCH₃ 37 Cl SO₂NH₂ 38 Cl SO₂NHCH₃

EXAMPLES 39 to 42

[0143] The symmetric 1:2 cobalt complexes of the compounds of thegeneral formula

[0144] in which the variables C and D are as defined in the table, canbe prepared analogously to those in Examples 2 to 4: Example No. C D 39H SO₂NH₂ 40 H SO₂NHCH₃ 41 Cl SO₂NH₂ 42 Cl SO₂NHCH₃

Dyeing Example 1

[0145] 10 parts of polyamide 6.6 woven fabric are dyed in 200 parts ofan aqueous liquor which comprises 0.27%, based on the fibre weight, ofdye mixture A according to Example 1A and is brought to pH 6 with aceticacid and sodium acetate. The dyebath is heated to 98° C. in the courseof 45 minutes, kept at 96° C. to 98° C. for 60 minutes and then cooledto 70° C. in the course of 15 minutes. The dyed woven fabric is thenremoved and rinsed and dried in the customary manner. A woven fabricdyed in a grey colour shade is obtained.

Dyeing Examples 2 to 7

[0146] The procedure described in Dyeing Example 1 is repeated, exceptthat the dye mixtures defined in column 2 in the following Table 1 areused in place of dye mixture A, affording polyamide 6.6 woven fabricsdyed in the colour shades defined in column 3. TABLE 1 Ex- ample Dyemixture Colour shade on polyamide 2 1.06% of dye mixture B brown 3 1.13%of dye mixture C brown 4 1.03% of dye mixture D brown 5 1.10% of dyemixture E brown 6 1.06% of dye mixture J brown 7 1.06% of dye mixture Lbrown

[0147] The procedure described in Dyeing Examples 1 to 7 is repeated,except that in each case corresponding dye mixtures which comprise thedye of the formula

[0148] in the same amount by weight in place of the dye of the formula(101) are used, affording polyamide 6.6 woven fabrics dyed in the colourshades defined in the particular examples.

Dyeing Example 8

[0149] 10 parts of polyamide 6.6 woven fabric are dyed in 200 parts ofan aqueous liquor which comprises 1.5%, based on the fibre weight, ofdye mixture F according to Example 1F and is brought to pH 6 withphosphate buffer (NaH₂PO₄/Na₂HPO₄). The dyebath is heated to 98° C. inthe course of 45 minutes and left at this temperature for 60 minutes.The dyed woven fabric is then removed and rinsed and dyed in thecustomary manner. A woven fabric dyed in a blue colour shade isobtained.

Dyeing Examples 9 to 12

[0150] The procedure in Dyeing Example 8 is repeated, except that thedye mixtures defined in column 2 in the following Table 2 are used inplace of dye mixture F, affording polyamide 6.6 woven fabrics dyed inthe colour shades defined in column 3. TABLE 2 Ex- ample Dye mixtureColour shade on polyamide  9 1.75% of dye mixture G blue 10 1.5% of dyemixture H blue 11 1.5% of dye mixture I blue 12 1.5% of dye mixture Kblue

[0151] The procedure described in Dyeing Examples 8 to 12 is repeated,except that in each case corresponding dye mixtures which comprise thedye of the formula (117) in the same amount by weight in place of thedye of the formula (101) are used, affording polyamide 6.6 woven fabricsdyed in the colour shades defined in the particular examples.

Dyeing Example 13

[0152] 10 parts of polyamide 6.6 fibre material (Helanca tricot) aredyed in 500 parts of an aqueous liquor which comprises 2 g/l of ammoniumacetate and 0.5%, based on the fibre weight, of the blue dye of theformula (118) according to Example 4 and is brought to pH 5 with aceticacid.

[0153] The dyeing time at a temperature of 98° C. is 30 to 90 minutes.The dyed polyamide fibre material is then removed and rinsed and driedin the customary manner. A piece of woven fabric which is dyedcompletely levelly in a blue colour shade and shows no material-relatedstripiness at all is obtained.

Dyeing Example 14

[0154] 10 parts of polyamide 6.6 yarn are dyed in 400 parts of anaqueous liquor which comprises 1.5 g/l of ammonium acetate and 0.5%,based on the fibre weight, of the dye of the formula (118) according toExample 4 and is brought to pH 5.5 with acetic acid. The dyebath isheated to 98° C. in the course of 30 minutes and kept at 96° C. to 98°C. for 60 minutes. The dyed yarn is then removed and rinsed and dried inthe customary manner. A yarn dyed in a blue colour shade is obtained.

What is claimed is:
 1. A dye mixture which comprises at least one 1:2cobalt complex dye of the formazan compound of the formula

in which X is substituted or unsubstituted C₁-C₈alkyl, phenyl, naphthyl,furyl or thienyl, R₁ and R₂ independently of one another are hydrogen orsubstituted or unsubstituted C₁-C₈alkyl, phenyl or naphthyl, m is anumber from 1 to 4 and the rings I, II, III and IV contain no furthersubstituents or are further substituted, together with at least oneanthraquinone dye of the formula (2)

in which Y is hydrogen or substituted or unsubstituted C₁-C₈alkyl,cyclohexyl, phenyl or 1,2,3,4-tetrahydronaphthyl and Z is substituted orunsubstituted C₁-C₈alkyl, cyclohexyl, phenyl or1,2,3,4-tetrahydronaphthyl, and in which the ring V of the anthraquinonedye of the formula (2) contains no further substituents or is furthersubstituted by one or two hydroxyl groups, or together with at least one1:2 chromium or 1:2 cobalt complex dye of two identical or different azocompounds from the group comprising compounds of the formulae (3), (4),(5) and (6)

in which R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ andR₁₆ independently of one another are hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, halogen, sulfo, hydroxyl, nitro, sulfamoyl orN—C₁-C₄alkylsulfamoyl, which is unsubstituted or further substituted inthe alkyl moiety by hydroxyl or C₁-C₄alkoxy.
 2. A dye mixture accordingto claim 1 , in which R₁ and R₂ independently of one another arehydrogen, C₁-C₄alkyl which is unsubstituted or substituted by hydroxylor C₁-C₄alkoxy, or phenyl which is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl,C₁-C₄hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl, nitro,sulfamoyl or N—C₁-C₄alkylsulfamoyl which is unsubstituted or furthersubstituted in the alkyl moiety by hydroxyl or C₁-C₄alkoxy.
 3. A dyemixture according to claim 1 , in which X and rings I, II, III and IV ofthe formazan compound of the formula (1) contain no further substituentsor are further substituted by C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl, C₁-C₄hydroxyalkylsulfonyl,halogen, sulfo, hydroxyl, carboxyl or nitro.
 4. A dye mixture accordingto claim 1 , in which the formazan compound of the formula (1) is acompound of the formula

in which R₁, R₂ and m are as defined in claim 1 ; and the phenylradicals of the compound of the formula (7) contain no furthersubstituents or are further substituted by C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl, C₁-C₄hydroxyalkylsulfonyl,halogen, sulfo, hydroxyl, carboxyl or nitro.
 5. A dye mixture accordingto claim 1 , in which m is the number 1 or
 2. 6. A dye mixture accordingto claim 1 , in which the formazan compound of the formula (1) is acompound of the formula

in which R₁ and R₁′ independently of one another are hydrogen orC₁-C₄alkyl and the phenyl radicals of the compound of the formula (8)contain no further substituents or are further substituted byC₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl,C₁-C₄hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl or nitro.7. A dye mixture according to claim 1 , which comprises, as theanthraquinone dye of the formula (2), an anthraquinone dye of theformula

in which Z₁ is phenyl which is unsubstituted or substituted byC₁-C₁₂alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, halogen,benzoylaminomethyl, chloroacetylamino, chloroacetylaminomethyl orα-chloroacryloylaminomethyl; phenyl-C₁-C₈alkyl, where the phenyl radicalcontains no further substituents or is substituted as defined for aphenyl radical Z₁ above; cyclohexyl which is unsubstituted orsubstituted by C₁-C₄alkyl, phenylsulfonylamino orC₁-C₄alkylphenylsulfonylamino; 1,2,3,4-tetrahydronaphthyl; or a radicalof the formula

in which W is a bridge member of the formula —O—, —NH—CO—, —OSO₂—,—NH—SO₂—, —CH₂—NH—SO₂— or —CH₂—N(CH₃)—SO₂—, R₁₇ is hydrogen, C₁-C₄alkyl,C₁-C₄alkoxy or halogen and R₁₈ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy,halogen or acryloylaminomethyl, Y₁ is hydrogen; C₁-C₄alkyl; phenyl whichis unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen;phenyl-C₁-C₈alkyl which is unsubstituted or substituted in the phenylring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or benzoylaminomethyl;cyclohexyl which is unsubstituted or substituted by C₁-C₄alkyl; or1,2,3,4-tetrahydronaphthyl, or an anthraquinone dye of the formula

in which Z₂ is phenyl which is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy or halo-en or cyclohexyl which is unsubstitutedor substituted by C₁-C₄alkyl or benzyl and Y₂ is C₁-C₄alkyl or is asdefined above for Z₂, or an anthraquinone dye of the formula

in which R₁₉ and R₂₀ are hydrogen or methyl.
 8. A dye mixture accordingto claim 1 , which comprises, as the anthraquinone dye of the formula(2), an anthraquinone dye of the formula


9. A dye mixture according to claim 1 , which comprises, as the 1:2chromium or 1:2 cobalt complex azo dye, a dye of the formula


10. A dye mixture according to claim 1 , which comprises 5 to 95% byweight of the 1:2 cobalt complex formazan dye, based on the total amountof dyes of the mixture.
 11. A symmetric 1:2 cobalt complex formazan dyeof a compound of the formula

in which R₂₁ is hydrogen, halogen or C₁-C₄alkylsulfonyl which isunsubstituted or hydroxyl-substituted and a) A₁ is a radical of theformula

B₁ is a radical of the formula

in which R₂₂ is hydrogen or unsubstituted or hydroxyl-substitutedC₁-C₄alkyl, R₂₂′ is hydrogen or C₁-C₄alkyl, R₂₃ and R₂₃′ independentlyof one another are each hydrogen, C₁-C₄alkyl or halogen, R₂₄ isC₁-C₄alkanoylamino or N—C₁-C₄alkylsulfamoyl which is unsubstituted orsubstituted in the alkyl moiety by hydroxyl, R₂₅ is hydrogen or halogenand R₂₆ is hydrogen, unsubstituted or hydroxyl-substituted C₁-C₄alkyl orphenyl which is unsubstituted or substituted by sulfo, carboxyl orsulfamoyl, or b) A₁ is a radical of the formula

B₁ is a radical of the formula

in which R₂₇ is hydrogen or halogen, R₂₈ is hydrogen or sulfamoyl andR₂₅ and R₂₆ independently are as defined above.
 12. A symmetric 1:2cobalt complex formazan dye according to claim 11 , in which R₂₁ ishydrogen, chlorine or 2-hydroxyethylsulfonyl, R₂₂ and R₂₂′ independentlyof one another are each hydrogen, methyl or ethyl, R₂₃ and R₂₃′independently of one another are each hydrogen, methyl, ethyl orchlorine, R₂₄ is acetylaminoe, propionylamino, N-methylsulfamoyl,N-ethylsulfamoyl or N-2-hydroxyethylamino, R₂₅ is hydrogen or chlorineand R₂₆ is hydrogen, methyl, ethyl, 2-hydroxyethyl or phenyl which isunsubstituted or substituted by sulfo, carboxyl or sulfamoyl.
 13. Asymmetric 1:2 cobalt complex formazan dye according to claim 11 , of acompound of the formula

in which R₂₁ is hydrogen, chlorine or fluorine, R₂₂ is hydrogen, methyl,ethyl or 2-hydroxyethyl, R₂₅ is hydrogen or chlorine and R₂₆ ishydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl, 2- or 3-carboxyphenyl,2- or 3-sulfamoylphenyl or 2- or 3-sulfophenyl.
 14. A symmetric 1:2cobalt complex formazan dye according to claim 13 , in which R₂₁ ishydrogen, chlorine or fluorine, R₂₂ is hydrogen, methyl or ethyl, R₂₅ ischlorine and R₂₆ is hydrogen, methyl, ethyl, 2-carboxyphenyl,2-sulfamoylphenyl or 2-sulfophenyl.
 15. A symmetric 1:2 cobalt complexformazan dye according to claim 11 , of a compound of the formula

in which R₂₁ is hydrogen or chlorine, R₂₂′ is hydrogen, methyl or ethyl,R₂₄ is N-methylsulfamoyl, N-ethylsulfamoyl or N-2-hydroxyethylsulfamoyl,R₂₅ is hydrogen or chlorine and R₂₆ is hydrogen, methyl or ethyl.
 16. Asymmetric 1:2 cobalt complex formazan dye according to claim 15 , inwhich R₂₁ is hydrogen, R₂₂′ is hydrogen, R₂₄ is acetylamino orpropionylamino, R₂₅ is hydrogen or chlorine and R₂₆ is hydrogen, methylor ethyl.
 17. A symmetric 1:2 cobalt complex formazan dye according toclaim 11 , of a compound of the formula

in which R₂₁ is hydrogen, methylsulfonyl, ethylsulfonyl or2-hydroxyethylsulfonyl, R₂₅ is hydrogen or chlorine, R₂₆ is hydrogen,methyl, ethyl, 2-sulfophenyl, 2-carboxyphenyl or 2-sulfamoylphenyl, R₂₇is hydrogen or chlorine and R₂₈ is hydrogen or sulfamoyl.
 18. Asymmetric 1:2 cobalt complex formazan dye according to claim 11 , of theformula

in which M^(⊕) is a cation.
 19. A 1:2 cobalt complex formazan dyeaccording to claim 18 , in which M^(⊕) is an alkali metal cation.
 20. Aprocess for the preparation of a symmetric 1:2 cobalt complex formazandye of a compound of the formula (51) according to claim 11 , whichcomprises diazotizing a compound of the formula B₁—NH₂   (57), couplingthe product to the hydrazone of the formula

and metallizing the resulting metal-free compound with a cobalt salt, inwhich the variables R₂₁, A₁ and B₁ are in each case as defined in claim11 .
 21. A process for dyeing or printing fibre material containinghydroxyl groups or containing nitrogen, which comprises the step ofapplying to said fibre material a tinctorial amount of a symmetric 1:2cobalt complex formazan dye according to claim 11 .
 22. A process fordyeing or printing fibre material containing hydroxyl groups orcontaining nitrogen with a dye mixture, which comprises the step ofapplying to said fibre material a tinctorial amount of a dye mixtureaccording to claim 1 .
 23. The process according to claim 22 , whereinnatural or synthetic polyamide fibre material is used as the fibrematerial.